Halogenated polymers containing complex epoxy fatty esters



3,281,382 HALUGENATED PULYMERS CONTAHNHNG COLEX EPUXY FATTY ESTIERSFrank E. Kuester, La Grange Park, and Thomas W. Findley, La Grange,1111., assignors to Swift 8; Company, Chicago, llll., a corporation oflllinois No Drawing. Original application Aug. 27, 1956, Ser. No.606,219, now Patent No. 2,978,463, dated Apr. 4-, 1961. Divided and thisapplication July 5, 1960, Ser. No.

13 Claims. (Cl. 260-23) have been prepared and their propertiesdescribed. According to one method generally used heretofore,unsaturated fatty acid esters of alcohols which may be natural materialssuch as animal and vegetable fats and oils are treated so that theethylenic groups (double bonds) are converted to epoxy groups withoutotherwise altering the molecular structure of the alcohol ester. It hasbeen generally assumed that the production of fatty epoxi-de or oxiranegroup-containing materials through interesterification in the presenceof an alkali catalyst of an epoxy ester and a non-epoxy ester would failto yield the desired product because of the fact that the epoxy fattycompounds react with an alkali catalyst as shown by Nicolet and Poulter,Journal of American Chemical Society 53, 1191 (1930), Bauer and Bahr inJ. Prakt. Chem. 122, 201-213 (1229), and Swern, US. Patent No.2,542,062.

Epoxy fatty esters produced by the epoxidation of correspondingunsaturated esters are often useful in preparing polyvinyl halide resinsdisplaying superior resistance to the effects of both heat and light. Ina resin such as polyvinyl chloride where an epoxy plasticizer is notpresent, the halogen is liberated from the resin thereby forminghydrogen chloride and an unsaturated bond in the resin itself. Thehydrogen chlorides tendency to catalyze further decomposition of theresin may result in a rapid darkening. This darkening may be inhibitedto a large extent by using an epoxy material, such as epoxidized soybeanoil, as a plasticizer instead of the type plasticizer conventionallyemployed; e.g. dioctyl phthalate which does little to prevent thisobjectionable darkening. However, even though it is possible to soprevent color deterioration, a marked stiffening and loss of flexibilityoccurs in polyvinyl chloride items plasticized solely with epoxymaterials such as epoxidized soybean oil, methyl epoxystearate andepoxidized acetylated monolein when exposed to severe aging conditions.This is in some instances at least due to loss of most of theplasticizer through bleeding from the resin. A partial solution isoffered by the conventional practice of selecting another plasticizersuch as dioctyl phthalate, butyl benzyl phthalate of tricresyl phosphateas the major plasticizer and using a lesser amount of an epoxy compoundas a secondary plasticizer whereby to secure the desirable stabilizingproperties of epoxy esters while minimizing the stiffening nited StatesPatent Patented @ct. 25, 1966 and bleeding to which the latter fallheir. This, of course, is not as convenient as simply admixing a singleagent With the polyvinyl chloride resin and is not always entirelyeffective.

Accordingly, it is an object of this invention to produce epoxy fattyesters by a process of transesterification or interesterificationemploying two esters, at least one of which is an ester of an epoxyfatty acid.

It is another object of this invention to provide a new group of epoxyfatty esters which exhibit good compatibility with the resin even afterprolonged. exposure.

It is another object of this invention to provide a proc ess for themanufacture of a mixture of substances which may be directly mixed witha polyvinyl halide resin to produce stable plasticized materials whichshow a resistance to darkening, loss of flexibility and bleeding.

Still another object of this invention is to produce mixtures ofcompounds which are efficient plasticizers for thermoplastic polyvinylhalide resins such as polyvinyl chloride and which are improved withregard to the bleeding and stiffening encountered in most epoxy fattyester plasticizers.

Further objects of this invention are to provide a plasticizer havinggood compatibility with polyvinyl halide resins and to provide aplasticized polyvinyl halide resin of improved stability.

Additional objects and advantages of this invention, if not specificallyset out, will become apparent to one skilled in the art during thecourse of the description which follows.

Broadly, this invention comprises a transesterification processemploying an epoxy fatty ester of a fatty chain length of eleven totwenty-two carbons and other organic or phosphoric acid esters; newepoxy esters of di or polyols produced thereby; a method of using theseproducts; and an unusually improved material which may result from theiruse on polyvinyl halide resins.

As stated above, according to what has heretofore been understood aboutepoxy compounds, oxirane groups present in the fatty acid portion of anester would be expected, on interesterification with a second ester, toreact with the alkaline interesterification catalysts. It has beenfound, however, that this is not necessarily the case.Interesterification may be carried out using a conventional alkalineinteresterification catalyst and the oxirane groups are found intact inthe product. This is true either of the materials being interesterifiedcontains one or more epoxy groupings and neither ester contains freecarboxyl groups. Any of the commonly used alkaline interesterificationcatalysts may seiye to promote the desired reaction. Preferred are themethoxide and ethoxides of the alkali metals potassium, lithium andparticularly sodium. Interesterification temperatures of between 50 C.and C. are satisfactory. Generally, a time of between about 1 and 4-hours at the temperatures given will be suflicient to effect theinteresterification desired. A catalyst must ordinarily be present inquantities of at least about .3% and the upper limit is generally thatemployed in ordinary interesterification processes where oxirane groupsare not present. Any two esters, at least one of which contains a fattyacid chain of eleven to twenty-two carbon atoms which itself containsone or more oxirane groups may be used in the interesterificationprocess of this invention. In its simplest form, the inventioncontemplates the interesterification of such materials as methyl epoxystearate and butyl acetate to yield butyl epoxy stearate. However, byselecting one of the materials to be interesterified from that group ofmaterials which are regarded as good primary plasticizers for polyvinylhalide resins and the other material from that group of fatty epoxyesters which are regarded as good. secondary plasticizers for suchresins, it is possible after interesterification to secure an epoxyfatty ester which is far superior to a simple physical mixture ofprimary and secondary plasticizers and performs the functions of bothunusually effectively. In addition to the esters customarily regarded asthe best primary plasticizers, certain esters which cannot be used asplasticizers because of their high volatility can be transformed byinteresterification into heavier molecules which are particularlyeffective as plasticizers, as shown in Examples XIII-XV, XX-XXII, XXVand XXVI appearing later in the detailed description of the invention.The reaction mixture containing a variety of compounds is preferablydirectly admixed to the vinyl halide resin to be plasticized inaccordance with customary practice.

More particularly, it has been found that contrary to what might beexpected, it is possible to employ an interesterification process forthe production of new epoxy fatty esters from two other esterscontaining no free carboxyl groups where one of these materials is anepoxy fatty acid ester without the opening of the oxirane ring. Theepoxy group or groups may be present on any ester having a fatty acidchain of a length between eleven and twenty-two carbons. Included andpreferred are the epoxidized animal, vegetable and marine oils such assoybean, lard and sperm oils, tallow, grease, rapeseed, linseed andsafilower oils and all available straight chain fatty materials, ofwhich methyl epoxy stearate is an example. Any ester of an epoxy fattyacid of proper chain length and a mono, di or polyol may serve in theinteresterification process. All free carboxyl groups of the epoxy estershould be entirely esterified. The non-epoxy starting materials whichmay be used comprise esters of organic acids and phosphoric acid.

The molar ratio of the materials undergoing interesterification willvary depending upon the materials selected and on whether the product,either a mono, di or polyol ester is to have only one or more of itsacid chain portions replaced by the new acid chain. For example, in theinteresterification of triacetin and methyl epoxy stearate between aboutone and three molar equivalents of the latter may be required for eachof the former depending on whether it is desired to replace one, two orall three of the acetate groups of the triacetin. Selection of theproper molar ratio in accordance with the well understood procedures forinteresterification is within the skill of anyone familiar with the art.

Examples of esters of di and polyols which enter into thetransesterification or interesterification reaction are the aliphaticand aromatic acid esters of such materials as ethylene glycol, propyleneglycol, ethyl hexandiol, butandiol, dodecandiol, diethylene glycol,dipropylene glycol, glycerol or polyglycerols, pentaerythritol, sorbitoland isomers and homologs of the above. Materials such as those listedabove having a fairly large molecule are preferred if the ultimateproduct is to be used as a plasticizer for polyvinyl halide films. Ifaliphatic acids, these acids are preferably saturated, either straightor branched chain, and have less than 11 car-hon atoms. Particularlysuitable aromatic acids are the benzoic and alkyl benzoic acids such astoluic or dimethyl benzoic acid. Esters derived from the above which areparticularly suitable are dipropylene glycol dibenzoate, diethyleneglycol dibenzoate, glyceryl triacetate, pentaerythritol tetrabenzoateand diglyceryl ether tetraacetate.

Examples of inorganic and organic acids which may be completelyesterified to produce the second ester used as a starting material areoxalic acid, fumaric acid, glutaric acid, pimelic acid, suberic acid,lactic acid, glycollic acid, tartaric acid, citric acid, succinic acid,adipic acid, azelaic acid, sebacic acid, phthalic acid, terephthalicacid, tetrahydroand tetrachlorophthalic acids, salicylic acid, benzoicacid and phosphoric acid, as well as the isomers and homologs of theabove. Those which are polybasic acids or mono basic aromatic acids areunusually effective as plasticizers for polyvinyl halides when combinedwith an epoxidized ester of a polyol. Particularly suitable estersderived from the above are tributyl phosphate, tricresyl phosphate,various alkyl aryl phosphate, diisooctyl phthalate, dioctylisophthalate, butyl benzyl phthalate, tributyl citrate and acetyltributyl citrate. Such materials, which have been used alone as primaryplasticizers, are advantageously employed in the transesterificationreaction of this invention to yield materials which are superiorplasticizers for polyvinyl halides.

As stated earlier, any of the commonly used alkaline interesterificationcatalysts may serve to promote the desired reaction. Preferred are themethoxides and ethoxides of the alkali metals such as potassium, lithiumand particularly sodium. A more complete list of the catalysts, organicand inorganic, may be found beginning at the bottom of column 4 of US.Patent No. 2,625,481 to Mattil et al., and beginning at the bottom ofcolumn 5 of US. Patent No. 2,625,483 also to Mattil et al.

Interesterification temperatures of between 50 C. and 130 C. areemployed. A temperature of about 75 C. to 110 C. is preferred for sodiummethylate. Of course, the most effective reaction temperature will varysomewhat depending upon the particular catalyst selected. Temperatureshigher than this for any appreciable time period result in extensivedecomposition of the oxirane groups. At lower temperatures, the reactionmay proceed very slowly, or the fats used may not be in a liquidcondition, preventing any reaction.

The time of treatment required to effect interesterification may alsovary somewhat depending upon temperature, concentration and the specificcatalyst selected and upon the particular reactants selected. As withall transesterification reactions, it may be stated as a general rulethat within an effective temperature range, the lower temperaturesresult in a decreased speed of reaction. A period of about two hours atC. to C. where sodium methylate is used as a catalyst has been foundadequate in most cases.

Theamount of catalyst used is in the general vicinity, but slightly inexcess, of that required for normal interesterification processes.Because of the aflinity of interesterification catalysts for moistureand because prolonged drying at excessively high temperatures is to beavoided if damage is not to be done to the oxirane ring, excess catalystmust be used. The exact amount of catalyst will be dependent on otherfactors, also, such as the free fatty acid content of the esters beingtreated. Generally, a minimum quantity of sodium methylate will be foundto be about 0.3% based on the weight of the mixture. When othercatalysts are employed, they should be added in suificient quantities toprovide about the molar equivalent of the sodium methylate which wouldbe necessary.

The mixture of complex esters or the purified high molecular weightepoxy fatty ester of a di or polyol with di or tri-basic acidscontaining no free carboxyl groups which can be obtained by properlyselecting the materials to be interesterified may combine in a singlemolecule the virtues of both a primary plasticizer and a fatty epoxide.Such a material, the preferred product for use as a single plasticizer,may have the following general structural formula:

where an epoxy fatty ester of ethylene glycol was interesterified with adi basic acid ester. In the formula above X and Y total between 7 and 18carbon atoms, R represents an alkyl or aryl group, and Z represents anyaliphat-. ic group.

A typical formula for the preferred plasticizer where a glyceride ispresent at the beginning of the interesterification reaction and thevalues of X, Y, Z and R are those given above is:

Preferably, one hundred parts of polyvinyl halide in a powdered form ismixed with 5 to 200 parts of this type of plasticizer. Normally,plasticizers are not used at levels above 100 parts per 100 parts ofresin. However, various applications require varying quantities ofplasticizer and the determination of proper amounts in accordance withwell known procedures is well within the skill of the art. To thismixture may be added small amounts of a stabilizer or lubricant, orboth, in accordance with conventional practice. The entire mixture ismilled on hot rubber rolls until the mass becomes semiliquid and can beremoved as -a uniform sheet.

Other suitable methods of fabrication of plasticized resins includeplastisol, organosol and extrusion. In plastisol formulation thepowdered resin is dispersed in the plasticizer along with anystabilizers and pigments or fillers to be used to form a liquiddispersion. This is then heated after application to fuse and solvatethe resin particles in the plasticizer. Upon cooling a flexible resinresults. In organosol formulations an organic solvent is used for theplasticizer and a liquid dispersion made as in plastisols. Prior tofusing the resin, the solvent is evaporated. The temperature and time ofheating necessary to obtain a strong and flexible film in plastisols andorganosols must be suificient to make the resin and plasticizerhomogeneous. For a plasticizer with good solvating characteristics lesstime or lower temperatures can be used than for one with poor solvation.Some of the compositions of this invention are of the proper chemicalstructure to be good in this respect as shown in the following examples.

In extrusion operations, a premix is first made of the plasticizer andresin, along with stabilizers, pigments, fillers, lubricant, etc. Inthis premixing operation good solvating properties such as shown by somecompositions of the following examples are beneficial in reducing thetime and temperature required to give a dry blend. This mixture is thenheated and extruded hot under pressure through a die of the shapedesired. The amount of physical work required can be reduced, orconversely, the resin can be extruded faster for the same physicalexpenditure if certain of the compositions of this invention are used.

Particularly suitable polyvinyl halide resins are Geon 101, Geon 103 EP,and Geon 121, manufactured by the B. F. Goodrich Chemical Company. Theseresins are homopolymers of vinyl chloride and diifer from one another inparticle size, density or molecular weight. Geon 101 and Geon 103 EP,are general purpose resins, while Geon 121 is designed primarily forplastisol or organosol applications. Geon 121 is described in ServiceBulletin PR-3, June 1954, of the B. F. Goodrich Chemical Co. Geon 103 EPis described in Service Bulletin 6-14, June 1954, of the same company.Geon 101 EP is described in Service Bulletin G-l, March 1950, of thesame company. Geon 121 is also described and claimed in U.S. Patent No.2,188,396. While Geon 121 is a particularly desirable plastisol-typeresin, the other Geon resins noted are preferred in the preparation ofrigid polyvinyl chloride resins.

The examples below show the preparation of various epoxidized esters bythe process of this invention. It is to be borne in mind that theseexamples are entirely for purposes of illustration and are not to beconstrued as placing limitations on the invention other than as setforth in the appended claims.

EXAMPLE I Interesterification of epoxidized soybean oil and butyl benzylphthalate A mixture of 1500 gm. of epoxidized soybean oil and 1500 gm.of butyl benzyl phthalate was dried for one hour under vacuum at C.Fifteen grams of sodium methoxide was added to the constantly stirredmixture after cooling to 110 C. The vacuum of 1520 mm. was reapplied andthe interesterification was allowed to continue for four hours. At theend of this period the reaction mixture was cooled and 30 ml. of 40%peracetic acid was added to inactivate the catalyst and effect a bleach.The peracetic acid treatment was carried out for one-half hour and wasfollowed by a one hour steam deodorization at 100110 C. and 15-20 mm.The residue from the steam deodorization was bleached with 3% BC. clayand 0.3% carbon for one-half hour and then filtered.

The analyses of the product and the initial epoxidized soybean oil arelisted below:

Epoxidized Interesteri- Soybean Oil fied Product 1.9 1. 5 181. 9 268. 89. 3 3. 3 Percent Oxirane Oxygen 6. 04 3. 04

Physical Mixture Interesterified Mixture Wt., g. Sap. No. Wt., g. Sap.No.

500 271. 5 500 268. 8 245 356. 0 278 263. 8 "Residue 184. 7 271. 1

Boiling Range 180-220 C. -240" C.

The analyses of the two fractions obtained from the physical mixtureindicate that the two original components, butyl benzyl phthalate andepoxidized soybean oil, have been effectively separated. However, in thecase of the interesterified product, the distillate is a mixturecontaining phthalic acid esters and fatty acid esters of monohydricalcohols. As shown by the saponification number, the residue from thisdistillation is the non-volatile glycerine-phthalic-epoxystearic acidesters including compounds of the following formulae:

7 S EXAMPLE IV OHZO-( J(CHZ)7 -OE CH(GHZ)7CH3 Interesterification 0fepoxidized lard oil 0 O with various esters g g 5 In the followingtableare listed the compositions of varlous mixtures of epoxidlzed lard011 and other esters prior to interesterification. Theseinteresterifications were accomplished using the same procedure asdescribed in Ex- O ample I. ornoii-oo.rr.

I Percent Percent Percent Epoxidized Dioctyl Butyl Benzyl Lard OilPhthalate Phthalate For convenience in writing structural formulae inthis 50 50 and the following examples, 9,10-epoxystearic acid has 80been used, although it is recognized that there can be 33 and are otherepoxy fatty acids present.

1 not s ow an in ication 0 de ositin an solid maoxirane oxygen. Thus,the distillate from the interesten- 20 terial upon prolosilged standingi mixtures such fied product contains volatile epoxy fatty acid esterswhich as described above except that the fatty acid esters fan beaccounted for only by the process of interesterificadude more Saturatednon epoxy fatty acids EXAMPLE II EXAMPLE V llll'e"estel'ificatioll 0fepoxidized soybean Oil Interesterification of epoxidized sperm oil anddloctyl Phthalale and butyl benzyl phthalate The following is a seriesof interesterifications carried The following are the compositions ofmixtures of the out involving epoxidized soybean oil (E50) and dioctylabove materials not to mteres r H a phthalate (DOP). In general theprocedure consisted of p ta 1 c non drying the mixture beforeinteresterification under vacuum at 110130 C. The sodium methoxidecatalyst was Percent Percent then added and the in'teresterificationallowed to cong i g g igi ig g yl tinue for a specified length of timeat IOU-110 C. The 3r a 6 catalyst was inactivated and the reactionproduct was 20 so bleached and filtered. Tabulated below are some of the50 interesterifications carried out in the laboratory with 20 analyticaldata on the products.

Percent Percent Percent Reaction Acid Percent ESO DOP NaOCH; Time, hrs.N0. Sap. N0. IV Oxrane The products in each case are light colored oilsand 5 are mixtures, in varying proportions, of octyl esters of epoxyfatty acids, octyl phthalate-epoxy fatty acid esters of glycerine, andsome unreacted dioctyl phthalate.

EXAMPLE III Interesterification of epoxidized soybean oil and butylbenzyl phthalate The fOnOW- The above products are light colored oilswhich tend to deposit a small amount of solid material when cooled to 0C. In each case, however, analysis shows that little or no epoxy oxygenhas been destroyed during the interesterification.

To the extent that sperm oil contains glycerides of fatty acids(12-30%), these compositions contain compounds of the epoxy fattyacid-phthalic acid-glycerine ester type similar to those described inthe previous examples. However, an important portion of the materialconsists of mixed esters of phthalic acid with epoxy fatty alcohols (C-C butyl or benzyl alcohols. In addition, there are butyl benzylphthalates and butyl and/or The products are light colored oils and aremixtures benzyl esters of epoxy fatty acids (C -C Removal containingcompounds of the type described in Example I. 75 of the latterconstituents as in Example I leaves essential- 9 1y mixed phthalicesters of epoxy fatty alcohols and lower alcohols.

In fashion resembling that set out in the foregoing Example V, an esterof a monobasic acid, such as methyl benzoate has been interesterifiedwith an alcohol ester such as epoxy octadecyl acetate. The chief productwas, in this case, the benzoyl ester of epoxy octadecyl alcohol.

EXAMPLE VI Interesterification epoxidized soybean oil and acetyletributyl citrate A mixture of 150 gm. of epoxidized soybean oil and 1550gm. of acetyl tributyl citrate were dried and subjected tointeresterification at 105110 C. for two and one-half hours in thepresence of 10 gm. of sodium methoxide. The catalyst was neutralized bythe addition of 20 ml. of 40% peracetic acid and then the mixture wasdeodorized at 120 C. for one hour. The isolated product had thefollowing analysis:

Acid No. 1.6 Percent oxirane ox. 2.93

The compounds obtained as a result of the interesterification decribedabove include butyl esters of epoxy fatty acids, acetylated epoxidizedglycerides, tributyl citrate ester of epoxy fatty acids andcitrate-glycerine-epoxy fatty acid esters some of which are representedby the following formulae:

The foregoing shows the interesterification process of this inventionusing a polybasic hydroxy acid and a polyol.

In similar fashion, the process of the invention has been carried outwith another polybasic hydroxy acid ester, tributyl acetyl citrate and amonohydric alcohol ester of a fatty acid, methyl epoxy stearate. Themethyl acetate was distilled off as it formed and a product containingthe tributyl citrate ester of epoxy stearic acid obtained. For a similarprocess using hydroxy acid, see Example XX.

EXAMPLE VII Epoxidation of interesterified esters of dioctyl phthalateand soybean oil Fifteen hundred grams [of dioctyl phthalate and 1500 g.of soybean oil were heated to 140 C. for one hour under a vacuum of 20mm. to remove any moisture or volatile material which might be presentin the mixture.

10 After cooling to 110 C. 30 gm. of sodium methoxide was added to theconstantly stirred mixture. The interesterificati-on was allowed toproceed for two hours. The product was washed with water to remove thecatalyst and any soaps formed during the reaction. The dried materialhad the following analysis:

Acid No. 0.3 Sap. No. "a 235.8 I.V. 63.2

Two thousand grams of the above interesterified product were epoxidizedusing 435 gm. of 50% hydrogen peroxide in the presence of 4.4 gm. ofconcentrated sulfuric acid and 39.0 gm. of formic acid (epoxidationprocess of copending application Serial No. 437,876). The expoxidationwas carried out at 40C. for twentyfour hours. After removing the excesshydrogen peroxide and acids by water washing, the product was dried andgave the following analysis:

Acid No. 0.4 Sap. N0. 231.7 I.V. 3.2 Percent Oxirane Ox. 3.2

and

Examples VIIIXX, XXIII, XXIV, and XXVI show the compatibility of theinteresterified products of this invention and polyvinyl chloride andother effects of the new product on polyvinyl halide material.

EXAMPLE VIII lnteresterified epoxy fatty esters as primary plasticizersIn order to give some indication that the interesterified products inthe foregoing examples are primary plasticizers, films plasticized withan interesterified mixture of epoxidized soybean oil and butyl benzylphthalate and with dioctyl phthalate were prepared and their physicalproperties compared. The interesterified mixture used in this examplehad an original composition of 53 butyl benzyl phthalate and 47%epoxidized soybean oil (see Example III).

The films were made up according to the following formula:

Parts Geon 103EP (polyvinyl chloride) 100 Plasticizer 4O Stabilizer(bariumcadmium-laurate) 2 Lubricant (mineral oil) 0.5

The ingredients were mixed in a Hobart Kitchen Mixer to form a uniformdry mix and then were compounded on a two-roll rubber mill at 320 F. for15 minutes. A film approximately 4 mils thick was taken off the mill.

After aging the films were tested and the results are tabulated below:

Dioctyl interesterified Phthalate Mixture Elmeudorf tear, gm./mil 300438 Tensile strength, p.s.i 3, 215 4, 280

Elongation, percent 200 280 Volatile loss (28 hrs. at 300 F.), percent23. 5 13 Heat Stability Test (hrs. to brown at 325 EXAMPLE IXCompatibility of interesterified epoxidized lard oil with polyvinylchloride Films of polyvinyl chloride were prepared on a rubber mill at300 F. using the following formulation:

Parts Geon 101 (polyvinyl chloride) 100 Plasticizer 67 Stabilizer(barium-cadmium laurate) 1.7 Lubricant (stearic acid) 1.7

The plasticizer used was an interesterified mixture of epoxidized lardoil and butyl benzyl phthalate at a level of 50% epoxidized lard oil. Atthe same time, a film plasticized with a physical mixture (notinteresterified) of epoxidized lard oil and butyl benzyl phthalate at alevel of 50% epoxidized lard oil was also prepared. When the films weresubjected to heat stability tests at 160 C. for 1, 2, 3, and 4 hours, nobleeding resulted (showing compatibility) and good heat stability(color, etc.) was observed in the case of the film plasticized with theinteresterified mixture. However, the film plasticized with the physicalmixture of epoxidized lard oil and butyl benzyl phthalate bled badly anddid not have as good heat stability.

The above tests were performed on films of the composition describedabove except that the plasticizers used were in one case aninteresterified mixture of 20% epoxidized lard oil and 80% butyl benzylphthalate and in the other .a physical mixture of the same comparison.The results of these tests were similar to the above in that theinteresterified product showed better compatibility and better heatstability than the physical mixture.

Thus, the results of these tests would indicate that the compatibilityof epoxidized lard oil (normally poor) with polyvinyl chloride has beengreatly improved by the interesterification process.

1 2 EXAMPLE x Compatibility of interesterified epoxidized soybean oilwith polyvinyl chloride Films of polyvinyl chloride were preparedaccording to the formulation in Example IX. Listed 'below is adescription of the plasticizers in the films.

Portions of the above films were subjected to oven heat of 160 C. andsamples were removed every hour until a period of four hours hadelapsed. These heat treated samples were labeled and then inspectedafter nine months aging. Visual inspection clearly indicated thesuperior heat stability of the films containing the epoxidizedplasticizers. However, all samples prepared using either epoxidizedsoybean oil alone or physical mixtures of epoxidized soybean oil anddioctyl phthalate showed an increasing amount of tackiness or exudationas the amount of epoxidized soybean oil in the plasticizer mixture wasincreased.

All the films plasticized with the interesterified mixtures showedimproved compatibility characteristics over films plasticized withcomparable physical mixtures. None of the films containing theinteresterified mixtures listed above showed any significant amount ofexudation of the plasticizer.

EXAMPLE XI Sun lamp irradiation of films plasticized with physical andinteresterified mixtures of butyl benzyl phthalate and epoxidizedsoybean oil Films plasticized with both physical and interesterifiedmixtures (Ex. III) of 50% epoxidized soybean oil and 50% butyl benzylphthalate were made up according to the following formulation:

Parts Geon 101 (polyvinyl chloride) Plasticizer 54 Stabilizer (di butyltin dilaurate) 3 Lubricant (stearic acid) 1 After compounding on arubber mill at 300 F. in the usual fashion, portions of the sheet werepress-polished. Samples of these films were exposed on a turntable to aGE. sunlamp for a period of eleven days. The distance from lamp tocenter of the turntable was six inches. Results were as follows:

Time, Physical Mixture Intcrcstcrified Mixture days 4 Lost surfacegloss, slight Good surface gloss, slight yellowing at center end.yellowing at center end. 8 More yellowing at center Slightly moreyellowing at en center end. 11 Dark yellow at center cud. Yellow atcenter and good surface gloss.

13 EXAMPLE x11 Comparison of interesterified and physical mixtures oftricresyl phosphate and epoxidized soybean Oil as polyvinyl chlorideplasticizers following formulation:

Parts Geon 121 (polyvinyl chloride) 100 Plasticizer 40 Stabilize-r(barium-cadmium *laurate) 2 Thinner 15 The above formulation was mixedfor fifteen minutes after addition of all the ingredients. Films werecast on plate glass using a 1.5 mil Bird applicator. The films were airdried for one hour and then fused for fifteen minutes in an oven at 325F. At the same time, films were prepared identically using as aplasticizer a physical mixture of fifty parts each of tricresylphosphate and epoxodized soybean oil. After aging twenty-four hours,tensile strengths on these films were run. Results are indicated below:

Interesteri- Physical fled Mixture Mixture Tensile Strength, p.s.i n 7,710 i 4, 400

In addition to greater tensile strength, the film made with theinteresterified product had much greater percentage elongation.

EXAMPLE XIII Epoxy fatty esters of dibutyl glycerophosphate Tributylphosphate and epoxidized soybean oil mixed in equal weights wereinteresterified for one hour with 1.1% catalyst and the product isolatedas previously described.

The product contained some unreacted tributyl phosphate and butyl estersof epoxy fatty acids and some glyceroph-osphate esters of epoxy fattyacids. It is desirable for some purposes to remove the tributylphosphate, but to illustrate the compatibility with polyvinyl chloridethe following mixture was milled on the rubber mill.

Parts Polyvinyl chloride (Geon 101) 100 Plasticizer prepared above 67Stabilizer (barium-cadmium laurate) 1.3

After milling for only five minutes at 300 F., a uniform film had beenformed which showed no signs of incompatibility on aging.

EXAMPLE XIV Volatility studies on films plasticized with interesterifiedand physical mixtures of dibutyl phthalate and epoxidized soybean oilAlthough dibutyl ph-thalate is not used to plasticize polyvinyl chloridedue primarily to its high volatility, it was interesterified Withepoxidized soybean oil. Prior to in-teresterification the mixture was43.5 parts of dibutyl phthalate and 56.5 parts of epoxidized soybeanoil. The interesterification was accomplished in two hours at 110 C. inthe presence of 0.5% sodium methoxide, The product was then isolated inthe method described in Example I.

'14 Films were prepared using this material and also a comparablephysical mixture as plasticizer according to the following formulation:

Parts Geon 101 (polyvinyl chloride) 100 Plasticizer 40 Stabilizer(barium-cadmium laurate) 2 The films were compounded on a rubber mill at300 F. and fuming was noted in each instance. After aging, portions ofeach film were placed in an oven at 330 F. for twenty hours. Both filmsstiffened as a result of this treatment, but only the film plasticizedwith the physical mixture shattered when bent. The weight loss from thefilm plasticized with the physical mixture was 35% whereas, the lossfrom the film plasticized with the interesterified product was 19%.

The purpose of tests set out in this example was to study thedifferences between the interesterified product and the simple mixtureof reactants. However, since there is still some free or unreacteddibutyl phthalate in the reaction mixture, it is desirable to removethis excess to further reduce the volatile loss. This product then is amixture of butyl esters of the epoxidized fatty acids and theglycerine-phthalic-epoxy fatty esters similar to those described inExample I. This product shows excellent plasticizing characteristics.

EXAMPLE XV Epoxystearoyl acetyl diethyl glycerophosphate 460 grams (1mol) epoxidized diacetyl glycerides derived from soybean oil accordingto the disclosure of copending application Serial No. 472,764, nowabandoned, was dried by heating at 140 C. under vacuum for one hour,mixed with freshly redistilled triethyl phosphate (364 grams, two moles)and sodium methoxide catalyst (5 grams) and held at C. under slightvacuum. Ethyl acetate distilled off and was collected. When one mol (97ml.) of ethy acetate was removed, the catalyst was killed by theaddition of a few milliliters of water and filtered off. The excesstriethyl phosphate was distilled off under vacuum and the last traces ofvolatile ester removed by steam distillation under vacuum.

The product was a yellow oil containing 5% phosphorus and 3% oxiraneoxygen. It contained mainly the mixed acetate-epoxy fatty acid esters ofdiethyl glycerophosphate.

A typical formula is:

i Hz0ll OCzH5 O-CzHs When this liquid is incorporated into a polyvinylchloride film by compounding on a rubber mill at 300 'F. for ten minutesa mixture of 100 parts Geon 101 and 50 parts of plasticizer (nostabilizer or lubricant), a flexible clear film results with highstrength and high elongation, good stability, and very low volatileloss. The film is flame resistant and the planticizer shows no tendencyto bleed on aging.

EXAMPLE XVI Citrate-glycerine epoxy fatty acid esters Theinteresterification product of Example VI was blended with Geon 101(polyvinyl chloride) to test compatibility and processability.Specifically, 40 parts of the interesterificati-on product, 60 partsGeon 101, 1 part stabilizer and 1 part lubricant were milled 10 minutesat 300 F. on a two roll mill. The film formed was clear and flexible andshowed no signs of incompatibility on aging.

1 EXAMPLE XVII Low plasticizer level The following compound was preparedto study the solvency effect of the plasticizer at low levels and toobserve the ease with which a relatively rigid compound could be milled.

The plasticizer was the same interesterified mixture of butyl benzylphthalate used in Example VIII. The ingredients were as follows:

Parts by wt. Polyvinyl chloride (Geon 103EP) 100 Plasticizer Stabilizer2 Yellow pigment dispersion /3 Lubricant /2 Milling temperature was 320F. and a sheet 67 mils thick was made. After aging the film showed atensile strength of 9100 psi. and a maximum elongation of 11%. It showedno color change on heating at 325 F. for four hours.

EXAMPLE XVIII High plasticizer level The following compound was made tostudy the cornpatibility of the plasticizer and strength of the film atvery high plasticizer levels.

The plasticizer was the same as in the previous example. The ingredientswere as follows:

Parts by wt. Polyvinyl chloride (Geon 101) 50 Plasticizer 100 Stabilizer/2 The mixture was well dispersed by one pass over a 3 roll mill andcast to make a film 15 mils thick by heating at 345 F. for 30 minutes.

A clear flexible film resulted with tensile strength of 1000 p.s.i. and450% maximum elongatiton. There was no evidence of bleeding ofplasticizer on aging.

EXAMPLE XIX Glycol di poxystearate interesterified with butyl benzylphthalate Epoxidized fatty esters other than the glycerides may be usedin the interesterification process and the resulting product may be usedas a plasticizer for polyvinyl chloride. Using the techniques previouslydescribed, one part of ethylene glycol diepoxystearate wasinteresterified with two parts of butyl benzyl phthalate in the presenceof 1% sodium methoxide. Films were prepared using the resulting productas the sole plasticizer according to the following formula:

Parts Geon 121 (polyvinyl chloride) 100 Plasticizer 40 Stabilizer 0.8Solvent (heptane) The above materials were thoroughly mixed and film ofapproximately 5 mil thickness was laid on a smooth glass plate. Afterair drying for one-half hour the film was cured for twenty minutes in anoven at 170 C. The cured film had good clarity and flexibility with notendency toward bleeding.

Normally glycol diepoxystearate is a solid at room temperature and is apoor plasticizer for polyvinyl chloride. When it is used as the soleplasticizer, the film has rather poor flexibility and upon aging exudesa solid material on the surface. The glycol diepoxystearate was notcompletely soluble in the butyl benzyl phthalate and had to be warmed to60 C. before the two materials became miscible. However, theinteresteriified mixture was homogeneous at room temperature and had tobe cooled to 10 C before any material precipitated out. r

A typical formula for the composition formed is as follows:

In addition, benzyl and/or butyl epoxystearate and unreacted butylbenzyl phthalate and glycol diepoxystearate are also present in theinteresterification mixture. It is apparent that the glycol ester formedis efiective as a plasticizer for polyvinyl chloride.

EXAMPLE XX Ester of a hydroxy acid and epoxidized soybean 01'! Twohundred grams of ethyl acetoxyacetate and 400 g. of epoxidized soybeanoil are heated at C. for onehalf hour for drying and then S g. of sodiummethoxide are added while the mixture is efficiently stirred. Theinteresterification is allowed to continue for two hours while refluxingthe volatiles formed. When the reaction period is completed the reactionmixture is filtered to remove the solid catalyst and then bleached with10 ml. of 40% peracetic acid for one-half hour. The mixture is vacuumstripped and steam deodorized at 110120 C. under vacuum for one hour.After bleaching with 2% clay and 0.5% charcoal, a light colored oil witha pleasant odor is obtained.

Films prepared as in Example XIX show the excellent plasticizingproperties of the mixed glycollate-epoxy fatty acid esters of glycerineformed above.

A typical formula for the ester formed is as follows:

There are also present ethyl and glycollate epoxy fatty acid esters aswell as other mixed glycerides.

EXAMPLE XXI Interesterification of triacetin and methyl epoxy stearateEXAMPLE XXII Interesterification of epoxidized lard oil with triacetinThe following example shows ratios of triacetin to epoxidized lard oilprior to addition of the catalyst:

Percent Percent ELO Triaeetin the products were isolated in the mannerpreviously described except those involving triacetin. Here the 17triacetin mixture was subjected to steam stripping under vacuum toremove the unreacted triacetin. All of the products were light coloredoils.

The preceding and Examples II-V show the variety of ratios of esters oneto another whereby to secure varying amounts of the desired componentsin the product.

The following examples show the preparation of a compound combining in asingle molecule an epoxy fatty group (or groups) and a benzoate group(or groups) with a glycerine or diglycol:

EXAMPLE XXIII Interesterification of epoxidized soybean oil withdiethylene glycol dibenzoate Eight hundred grams of epoxidized soybeanoil and 800 grams of diethylene glycol dibenzoate were dried undervacuum for one-half hour at 105 C. After the drying period, 16 grams ofsodium methoxide were added to the constantly stirred mixture and theinteresterification allowed to proceed for two hours at the abovetemperature. When the reaction period was completed, the catalyst wasneutralized and the interesterified mixture isolated by deodorizationand filtration.

The product obtained 'by interesterification is a mixture more complexthan it was prior to interesterification. Listed below are some of thepossible structures obtained in the mixture in addition to small amountsof the original materials:

The product, a mixed benzoate-epoxystearate of diethylene glycol, is alight yellow oil with a faint pleasant odor.

O n) O Films of polyvinyl chloride using the interesterified product asplasticizer were prepared by milling in a tworoll mill at 300 F. for 15minutes the following mixture:

Parts Polyvinyl chloride resin (Geon 101) 60 Plasticizer Stabilizer(barium-cadmium laurate) 1 Lubricant 1 The film was clear and flexibleand showed no sign of bleeding after six months.

A similar mixture was also prepared using dipropylene glycol dibenzoatein the above procedure. The results were quite similar.

EXAMPLE XXIV Benz yl diglycol epoxy stearate A mixture of diethyleneglycol dibenzoate (314 grams, one mol) and methyl epoxystearate (313grams, one mol) is heated under vacuum at 140 C. for one hour to removeany possible trace of moisture, then cooled to 100 C. and sodiummethoxide catalyst-(4 grams) added. Heating at this temperature iscontinued fior four hours while lowering the pressure to about 1-2millimeters of mercury. Methyl benzoate is removed during thisoperation, and the last traces are removed by a further steamdeodorization after filtration to remove the spent catalyst.

EXAMPLE XXV Iltteresterification of epoxidized soybean oil and triacetinFifty par-ts of epoxidized soybean oil and 50 parts of triacetin werein-teresterified in the presence of 1% sodium methoxide at 110 C. forone hour. After the catalyst was deactivated the reaction mixture wasdeodorized at -135 C. to remove the unreacted triacetin. Analysis of theproduct is listed below:

Acid No. 0.95 Sap. No. 428.0 I.V. 4.6 Percent ep. ox. 3.55

The product is a mixture of the diacetyl and monoacetyl derivatives withsome ninreacted triacetin.

The last example below shows the process of this in vention usingvolatile esters.

EXAMPLE XXVI Interesterification of epoxidized soybean oil with ethylacetate and N-amyl acetate When volatile esters are involved in 'anintcresterification with epoxidized soybean oil, the procedure is ingen: eral the same as described in Example I. The exception is thatduring the interesterifioation, care should be taken that none of thevolatile ester is removed from the Percent Re- Epoxidized Ester Percentaction Reaction Soybean NaOCH; Time, Temp.

Oil hrs.

42 I, Ethyl Aeetateun. 1.0 2 Reflux Temp. 40 n-An1ylAeetate 1. 6 2 110C.

The composition of the reaction product :after removal of the volatileester is a mixture of the monohydric alcohol esters of epoxy fattyacids, and acylated mono-, and diglycerides of epoxidized soybean oil.These compositions are useful as low temperature plasticizers forpolyvinyl chloride.

As indicated above, it has been found that unusually effectiveplasticizin-g results are secured in accordance with the teachings ofthis invention in halogen-containing resins generally. And there areother advantages in the use of these complex esters too. As shown inExamples VIII and XII, certain of the new compositions bring outimproved tensi-le characteristics when incorporated into polyvinylchloride resins. They may also facilitate processing. The resultstabulated and set forth under the heading Example VIII show that bothstrength and maximum elongation are increased where the interesterifiedcomposition is employed instead of an ordinary primary plasticizer, suchas dioctyl phthal-ate. This is unusual, for it is generally anticipatedthat plasticizers which have a beneficial effect on maximum elongationadversely influence film strength.

The epoxy fatty acid-phthalie acid-glycerides of Example VIII also showunusually rapid dry mixing when mixed with powdered polyvinyl chlorideresin. In addition, extrusion of film is possible at an unusually rapidrate operating at unusually low temperatures, although exceptionallyhigh die temperatures can be used. This allows for greater rate ofproduction, with less frequent shut downs for cleanup of charredmaterial.

Unusual results are also observed where the tensile strength and maximumelongation of the product of Example XII is tested. It is believed thatthe improved results here may be due to the ease of solvation of theresin by the interesterified plasticizer.

The compositions of Examples XXIII and XXIV share most of the advantagesof the preferred plasticizers for polyvinyl halides; specifically,greater heat and light stability without sacrificing compatibility andlow volatility with good tensile properties. This was not expected to bethe case as the acid protions of the esters are not derived frompolybasic acids. However, it is helived that the fact that the acidportion is derived from an aromatic acid having a large size and asubstantial molecular weight is the explanation for the improved resultsobtained.

While the preferred resin is the comm-on polyvinyl chloride, otherswhich may be employed are those which are also made from vinyl compoundssuch :as vinylidene chloride, vinyl chloracetate, chloro styrenes andchloro butadienes. Such vinyl compounds can be polymerized singly or inadmixture with these or other halogen containing vinyl compounds or withvinyl compounds free from halogen. For example, there are a large numberof unsaturated materials which are 'free from halogen and which may becopolymerized with halogen-containing vinyl compounds; e.g. vinyl estersof carboxyl-ic acids vinyl acetate, vinyl propionate, vinyl butyrate,and vinyl benzo ate. Esters of unsaturated acids which may serve aremethyl acrylate, allyl acrylate and the corresponding esters ofmethacrylic acid. Vinyl aromatic compounds which are suitable arestyrene, para-ethyl styrene, divinyl benzene, vinyl naphthalene, andalpha-methyl styrene. Other unsaturated materials which serve are thedienes such as but-adiene, unsaturated amides such as acrylic acidamide, acrylic acid anilide, unsatuarted nitriles, such asacrylonitrile; esters of alpha-beta-unsaturated carboxylic acids as forexample, the methyl, ethyl, propyl, butyl, any], hexyl, heptyl, octyl,allyl and rnethallyl and the phenyl esters of rnaleic, crotonic,itaconic, fumanic acids and the like. However, it is preferred to formthese 00- polymers from substances which contain at least 50% by weightof a halogen-containing vinyl compound such as polyvinyl chloride.

The plasticizers to which this invention is directed are alsoparticularly effective when intimately admixed with halogen-containingresins in which part or all of the halogen is introduced into preformedresin. For example, chlorinated polyvinyl acetate, chlorinated polyvinylstyrene, chlorinated polyvinyl chloride, chlorinated natural andsynthetic rubbers such as rubber hydrochloride are particularlysuitable. The plasticizer should, however, always be added afterintroduction of the halogen.

While attention has been directed entirely to chlorinecontaining resins,it is to be borne in mind that resins containing halogens other thanchlorine such as bromine, fluorine and iodine may also be formed and towhich these plasticizers may be added with beneficial results.

While it is entirely possible to use pure esters as starting materials,it is most feasible from the standpoint of raw materials cost to usemixtures which occur in various natural oils, as for example, linseed,castor, soya bean, perilla, corn, cotton-seed, sunflower, safflower,sesame, poppy, walnut, peanut, olive, rapeseed and whale oil.

It is seen therefore that by following the teachings of this invention,it is possible to produce a plasticizer for vinyl halide resins fromreadily available organic compounds which has decided superiority to theconventional physical mixtures of primary and secondary plasticizers.The compositions show improved compatibility with vinyl halide resinsand decreased tendency to bleed out or volatilize. The plasticizedresins secured display improved heat and light stability and good colorand they are prepared with ease. Further, as can be seen by reference tothe examples, the resulting polyvinyl halide resins may possess otherunusual properties, for example, improved tensile strength and tearstrength, and ability to tolerate a much greater degree of elongationthan can polyvinyl halide resins plasticized with a simple physicalmixture of primary and secondary plasticizers of the type used asstarting materials for reaction of this invention.

By fatty acids as used herein, it is intended to include all acidsnormally included with the term including the straight or branched chainsubstituted or unsubstituted aliphatic acids; by organic acid orcarboxylic acid, as used herein, it is intended to include all aliphaticand aromatic acids and hydroxy acids containing one or more COOH groups;and by the prefix poly it is intended to indicate the presence of two ormore of the groups under consideration. For example polybasic acidrefers to an acid containing two or more carboxyl groups and polyolrefers to an alcohol containing two or more hydroxyl groups. Where theterm functional group is used herein with relation to acids and alcoholsand their esters it is intended to include the group of an alcohol andthe (f-OOR group of an acid wherein the symbol R referes to an aryl,alkyl or an acyl group or a hydrogen atom.

Obviously, many modifications and variations of the invention ashereinbefore set forth may be made without departing from the spirit andscope thereof, and therefore only such limitations should be imposed asare indicated in the appended claims.

We claim:

1. A composition of matter comprising: a mixture of a polyvinyl halideresin and an epoxy fatty acid ester of an aliphatic polyol selected fromthe group consisting of glycol and glycerol, the fatty acid chain lengthof which is 11 to 22 carbon atoms, said polyol having at least onehydroxyl group esterified with an acid selected from the groupconsisting of polycarboxylic aliphatic acids, aromatic acids, hydroxycarboxylic acids, and phosphoric acid, substantially all free acidgroups being completely esterified.

2. The composition of claim 1 wherein the acid is phthalic acid andwherein the remaining carboxyl group of said acid is esterified with anoctyl group.

3. The composition of claim 1 wherein the acid is phosphoric acid andwherein the remaining acid groups of said acid are esterified withcresyl groups.

4. The composition of claim 1 wherein the polyol is glycerine.

5. The composition of claim 1 wherein the polyol is polyethylene glycol.

6. The composition of claim 1 wherein the acid is henzoic acid.

7. A composition of matter comprising: a mixture of a polyvinyl halideresin and an epoxy fatty acid ester of glycerine, the gatty acid chainlength of which is 11 to 22 carbon atoms, said glycerine having at leastone hydroxyl group esterified with a member selected from the groupconsisting of polybasic aliphatic acids, aromatic acids, hydroxy acidsand phosphoric acid substantially all 22 additional acid groups of saidacid being completely esterified.

8. The composition of claim 7 wherein the fatty ester of glycerine isderived from soybean oil.

9. The composition of claim 7 wherein the fatty ester of glycerine isderived from lard oil.

10. The composition of claim 7 wherein the fatty ester of glycerine isderived from sperm oil.

11. The composition of claim 1 wherein the acid is phthalic acid andwherein the remaining carboxyl group of said acid is esterified with abatyl group.

12. The composition of claim 1 wherein the polyol is ethylene glycol.

13. The composition of claim 7 wherein the fatty ester of glycerine isderived from linseed oil.

References Cited by the Examiner UNITED STATES PATENTS 2,485,160 10/1949 Niederhauser et al. 260-23 2,745,846 5/1956 Dazzi 260-23 2,786,0393/1957 Dazzi 26018 2,809,177 10/1957 Shokal 26018 2,889,338 6/1959 Dazzi260-458 2,895,966 7/1959 Ault et a1 260-23 2,956,969 10/ 1960 Havens260-23 2,963,455 12/ 1960 Rowland et al 26023 2,971,012 2/1961 Wolif260--23 3,112,294 11/1963 Newey 26018 MURRAY TILLMAN, Primary Examiner.

ALFONSO D. SULLIVAN, LEON I. BERCOVITZ,

MILTON STERMAN, Examiners.

G. F. LESMES, P. P. GARVIN, T. D. KERWIN,

Assistant Examiners.

UNITED STATES PATENT OFFICE Certificate of Correction Patent No.3,281,382 October 25, 1966 Frank E. Kuester et :11.

It is herelay certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 5, lines 5 to 12, in the formula, the upper right-hand portion ofthe formula reading )CH ,CH read (CH CH same formula, for the extremelower right-hand portion reading OX read -OZ column 6, lines 65 to 75,the upper right-hand portion of the formula reading CH CII read (CH CHsame formula, the extreme right-hand portion of the formula reading H Cread CH column 9, line 12, for 150 read 1556; line 24, for deoribed readdescril)ed--; same column 9,11nes 40 to -15, for that portion of theformula reading COOCJI read (TOOC H column 11, line 68, for comparisonread composition; column 14, line 2, for plasticizm read plast1c1zers;line 3.), for ethy read ethyl; column 15, line 39, for "clomgmtn'on readelongat1on; columns 17 and 1S, hues 29 to in, the extreme lowerrightehand portion ol the formula reading CH read CH column 19, line 55,for protions read portions; column 20, line 39, for mixtures readmixture,; column 21, line 31, for gatty read fatty-; in the LettersPatent only, after column 16, insert columns 17 to 20.

Signed and sealed this 28th day of November 1967.

[SEAL] Attest:

EDWARD M. FLETCHER, JIL, EDWARD J. BRENNER: Attesting Oflicer.Commissioner of Pazenta'.

1. A COMPOSITION OF MATTER COMPRISING: A MIXTURE OF A POLYVINYL HALIDERESIN AND AN EPOXY FATTY ACID ESTER OF AN ALIPHATIC POLYOL SELECTED FROMTHE GROUP CONSISTING OF GLYCOL AND GLYCEROL, THE FATTY ACID CHAIN LENGTHOF WHICH IS 11 TO 22 CARBON ATOMS, SAID POLYOL HAVING AT LEAST ONEHYDROXYL GROUP ESTERIFIED WITH AN ACID SELECTED FROM THE GROUPCONSISTING OF POLYCARBOXYLIC ALIPHATIC ACIDS, AROMATIC ACIDS, HYDROXYLCARBOXYLIC ACIDS, AND PHOSPHORIC ACID, SUBSTANTIALLY ALL FREE ACIDGROUPS BEING COMPLETELY ESTERIFIED.